Title : PHOTOCHEMISTRY AND FREE-RADICAL REACTIONS IN FORMAMIDE VAPOUR,

Corporate Author : NATIONAL RESEARCH COUNCIL OF CANADA OTTAWA (ONTARIO) DIV OF CHEMISTRY

Personal Author(s) : Boden,J. C. ; Back,R. A.

Report Date : 28 MAY 1969

Pagination or Media Count : 9

Abstract : The photolysis of formamide vapour has been studied at temperatures from 115 to 400C and pressures from 8 to 50 torr, with 206.2 nm radiation. Products detected were CO, H2, and NH3, with quantum yields at 150C of 0.8, 0.6 and 0.2 respectively. From experiments with added ethylene and with NH2CHO and ND2CHO, it was deduced that there were three major primary processes. The reactions of CH3 with NH2CHO, ND2CHO and NH2CDO were also studied, and approximate Arrhenius parameters were obtained. Hydrogen was abstracted almost exclusively from the formyl position, and the deuterium isotope effect was about 6. Below 200C, NH2CO radicals were thermally stable, but at higher temperatures they decomposed leading to a chain reaction. Approximate Arrhenius parameters were estimated for this decomposition, which was found to be pressure dependent. (Author)